Process for improving granulated detergents

ABSTRACT

A process for improving the properties of granulated detergents, comprising adding a liquid perfume or lower alcohol to the granulated detergent produced by the spray drying method while making the detergent grains roll over, and subsequently adding thereto metallic soap powder having a mean particle diameter of less than 100 Mu when the surface of detergent grain has been imparted with a sufficient adhesive power by virtue of the adhesion of said liquid perfume or lower alcohol thereto.

United States Patent [1 1 Takenouchi et al.

[ PROCESS FOR IMPROVING GRANULATED DETERGENTS [75] Inventors: KuniyoshiTakenouchi, Funabashi;

Norihiro Ohno, Chofu; Fusao Kondo, Chiba, all of Japan [73] Assignee:Lion Fat & Oil Co., Ltd., Tokyo,

Japan [22] Filed: June 27, 1974 [21] Appl. No.: 483,806

[30] Foreign Application Priority Data July 4, 1973 Japan ,4 48-74863July 4, 1973 Japan 48-74864 [52] US. Cl. 252/92; 252/384; 427/212;427/214 [51] Int. Cl. CllD 17/00 (58] Field of Search 252/91, 92, 381,384;

[56] References Cited UNITED STATES PATENTS 2,932,556 4/1960 Stephanou252/384 1 Dec.9,1975

Otrahalek l 17/ 100 Binsley 252/384 FOREIGN PATENTS OR APPLICATIONS22,789 1929 Australia 252/381 Primary Examiner-William E. SchulzAttorney, Agent, or Firm-Woodhams, Blanchard and Flynn 1 ABS'IRACT 4Claims, No Drawings PROCESS FOR IMPROVING GRANULATED DETERGENTSBACKGROUND OF THE INVENTION a. Field of the Invention The presentinvention relates to a process for improving the properties ofgranulated detergents produced by the conventional spray drying methodso as to make them retain the excellent fluidity, hygroscopicsolidification preventability and stable preservability over a longperiod of time and also stabilize the imparted perfume.

b. Description of the Prior Art The majority of the prevailinggranulated detergents are those manufactured by the spray drying method(that is, a method of obtaining dried grains in a short time bycontacting sprayed particles of a material slurry with a hot air, whichemploys either the parallel-current process or the counter-currentprocess in effecting the contact between said particles and hot air)suitable for mass production. Among these granulated detergents, theso-called detergents for domestic use are ones prepared by the spraydrying method and further adding some perfume by spraying in the stateof liquid thereafter. However, the thus prepared detergents for domesticuse have been defective in that the fragrance is apt to diminish in arelatively short period of time and fail to last long.

Besides, though the conventional granulated detergents of the foregoingtype have a satisfactory watersolubility, they are attended withtroubles in respect of the hygroscopic solidification preventabilitythereof, entailing some trobles in respect of the stable preservability.The hygroscopic solidification preventability herein means the pro; ertyof detergent grains to be free of solidification of absorbing moisturein the air. In other words, a granulated detergent superior inhygroscopic solidification preventability means such one as will hardlyabsorb or never absorb moisture in the air and will maintain a granularshape without getting solidified over a long period of time. Theconventional granulated detergents are inferior in said hygroscopicsolidification preventability so that hygroscopic solidification wouldtake place even after packing thereof in a carton case. Even in the casewhere such solidifica tion is somehow controlled, the fluidity of thedetergent grains per se is poor, entailing in troubles on the occasionof taking out of the storing silo or packing in the carbon case.

As a measure for overcoming these defects in the prior art, thespecification for US. Pat. No. 3,472,784, for instance, has disclosed amethod of obtaining a granulated detergent by adding surface activeagent and water to such inorganic builders for use in detergent assodium tripoliphosphate, soda ash, etc. while admixing them by a ribbonmixer. And it is proposed to coat, the surface of detergent grainsuniformly with tripoliphosphate, soda ash or sodium sulfate. However,even these method has failed to produce a satisfactory granulateddetergent as desired. Not only that, it has made no contribution to theimprovement of the fragrancy required especially of the granulateddetergents for domestic use in general.

SUMMARY OF THE INVENTION One object of the present invention is toprovide a process for improving the fluidity and the hygroscopic 2solidification preventability of granulated detergents. Another objectof the present invention is to provide a process for an everlastingstable fragrance to said granulated detergents.

In other words, the process for improving the properties of granulateddetergents according to the present invention is characterized by thesteps of adding a lower alcohol or liquid perfume as the binder to thesurface of every grain of an ordinary granulated detergent prepared bythe spray drying method while making the grain roll over, andsubsequently adding thereto a specific metallic soap powder when thesurface of detergent grain has been thus imparted with a sufficicntadhesive power, thereby letting said metallic soap powder adhere to thesurface of detergent grain.

To be more precise, the application of said lower alcohol (mainly by thespray method) to the granulated detergent is for the purpose ofimparting adhesive power to the surface of detergent grain so as tofacilitate satisfactory adhesion of said metallic soap powder thereto.And, the application of said liquid perfume (mainly by the spray method)to the granulated detergent is for the purpose of imparting adhesivepower to the surface of detergent grain to thereby not only facilitatesatisfactory adhesion of the metallic soap powder thereto but alsoperpetuate the fragrance of the granulated detergent. Employment ofwater as the binder in place of said lower alcohol or in place of saidliquid perfume with a view to coating the detergent grains with metallicsoap powder would fail to achieve the aimed effect because the metallicsoap is poor in affinity with water so that a uniform coating of thesurface of detergent grains with metallic soap powder is infeasible.And, employment of inorganic builders for use in detergent such assodium tripoliphosphate and sodium sulfate in place of said metallicsoap powder would also fail to achieve the aimed effect. There havehitherto been proposed various methods for securing the perpetuity offragrance of granulated detergents, but none of these methods has everadopted the rolling-granulation process applied for film coating like inthe present invention and has been successful in overcoming theabove-mentioned defects simultaneously.

The object of the present invention can be achieved subject toapplication of a lower alcohol or liquid perfume as the binder andapplication of metallic soap powder as the coating agent. The reason whysuch as effect as in the present invention can be brought about is yetto be clarified: nevertheless, it is presumed that, by virtue of synergybetween the water insolubility and water repellency possessed by saidmetallic soap powder and the proper affinity with metallic soappossessed by said lower alcohol and liquid perfume, the metallic soappowder might uniformly adhere to the surface of detergent grains to forma coating. Particularly in the case where a liquid perfume is employedas the binder, said perfume is distributed into the inner part of theproduct and coated the surface so that the perpetuity of fragrance canbe secured. Besides, at the time of use of the product, as a result ofbreakdown thereof, the fragrance becomes greater. Because of the surfaceof every detergent grain having been uniformly coated with metallicsoap, the product granular detergent dis plays an improved fluidity andhygroscopic solidification preventability.

The lower alcohol applicable to the present invention is monohydricalcohol or dihydric alcohol having l-4 carbon atoms. Such alcohols maybe used either individually or upon combining two or more of them. Theappropriate amount of the lower alcohol to be applied is in the range of0.1-1 part by weight relative to l parts by weight of detergent grains:in case of application of less than 0. l part by weight, the surface ofdetergent grain fails to get wet sufficiently, while in case ofapplication of more than I part by weight, it is rather unfavorable asit will require such additional processes as drying and recoveringalcohol. As to the liquid perfume for use in the present invention, anyperfume commonly used in the granulated detergents for do mestic use isapplicable as long as it has a proper affinity with metallic soap to becoated on the layer of perfume adhering to the detergent grain, and itincludes, for instance, terpene series (linalool, terpineol, geraniol)phenol series (eugenol) and aromatic alcohol series (phenylethylalcohol, benzyl alcohol). Such liquid perfumes may be used eitherindividually or upon combining two or more of them. The appropriateamount of the liquid perfume to be applied is in the range of 005-1 partby weight relative to 100 parts by weight of detergent grains.

The metallic soap powder applicable to the present invention is calciumsalt or magnesium salt of saturated fatty acid having a mean particlediameter of less than 10011.. However, in the case where lower alcoholis employed as the binder, it is necessary to apply a fatty acid salthaving l6-20 carbon atoms. Application of a metallic soap powder havinga mean particle diameter of more than 100;]. is inadvisable as it willnot only necessitate the use of metallic soap powder in great quantitiesin order to achieve the intended effect but also spoil the appearancesof the resulting product. The foregoing metallic soap powders may beused either individually or upon combining two or more of them. Theappropriate amount of the metallic soap powder to be applied is in therange of 0.3l parts by weight preferably 0.5-10 parts by weight relativeto I00 parts by weight of detergentgrains: in case of application ofless than 0.3 part by weight, the surface of detergent grain fails to beuniformly coated therewith, while in case of application of more thanparts by weight, the amount is excessive and the water-insolublemetallic soap turns into a white emulsion when the product granulardetergent is dissolved in water, so that it is undesirable.

The granulated detergent constituting a material for use in the processaccording to the present invention suffices to be ordinary hollow grainsobtained by spraying and drying a detergent composition, and is notlimited to any particular detergent. In other words, the materialgranulated detergent consists of the surface active agent, inorganic ororganic builder, fluorescent agent and other additives.

The rolling apparatus for use in the process according to the presentinvention is not limited to any particular one; that is, any of thewell-known apparatuses can be employed. For instance, it will do employthe conventional rolling-drum for use in adding perfume in the field ofdetergent-manufacturing industry. Addition of the lower alcohol orliquid perfume may be performed by any method as long as uniformaddition can be effected thereby; nevertheless, the spray method, andespecially the nozzle-spray method employing solid cone nozzle, hollowcone nozzle and the like, are suitable. As to the method for adding themetallic soap powder, any method will do as long as uniform coating canbe ef- 4 fected thereby; for instance, the sprinkling method may beapplied.

Next, the concrete procedures for obtaining an improved granulateddetergent as product according to the process of the present inventionwill be elucidated in the following, but it will be understood thatvariations and modifications thereof which lie within the scope of theinvention as defined by the appended claims are fully contemplated.

To begin with, the material hollow-granular detergent is introduced intoa rolling-drum. Thereafter, a prescribed amount of lower alcohol orliquid perfume is added to said granular detergent in the drum by anappropriate method, such as nozzle-spraying, while rolling the drum.When said lower alcohol or liquid perfume has sufficietly adhered to thesurface of all detergent grains to make them wet, a prescribed amount ofmetallic soap powder is added to the thus wetted detergent grains by anappropriate method, such as sprinkling, so as to make said powderuniformly adhere to said grains. The inside temperature of the drumshould of course not be so high as to permit said lower alcohol orliquid perfume to boil or evaporate. Accordingly, on the occasion ofemploying a granulated detergent im mediately after being produced bythe spray drying method as the material for use in the presentinvention, inasmuch the detergent grains still hold a high temperature,if said temperature is so high as to permit the lower alcohol or liquidperfume to boil or evaporate, the material granulated detergent must beonce cooled.

The present invention renders it possible to achieve the desired effectby simple procedures, so that the operation can be performedcontinuously and is therefore suitable for mass production.

DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLE 1.

parts by weight of a hollow-granular detergent having the followingcomposition as obtained by the spray drying method were introduced intoa rollingdrum. 0.5 part by weight of ethanol was added to said detergentby the use of a spray nozzle at the inlet of the drum while rolling itto see that said ethanol be applied to the detergent grains uniformly.When the detergent grains were sufficiently wetted with the prescribedamount of ethanol, 1 part by weight of calcium stearate having a meanparticle diameter of less than 20;]. was sprinkled over the thus wetteddetergent to make it adhere and form a coating thereon. The insidetemperature of the drum on this occasion was 35C.

When the fluidity and the hygroscopic solidification preventability ofthe granular product thus obtained were examined after leaving saidproduct standing for 24 hours, the results were as shown in Table-l inthe following.

Composition of the material hollow-granular detergent:

sodium linear alkylbenzene sulfonate sodium tripolyphosphate sodiumsilicate sodium sulfate fluorescent agent CMC (carboxymethyl cellulose)water EXAMPLE 2.

A granular detergent product was obtained through the same procedures asin Example 1 except for substituting a perfume (namely, geraniol) forethanol. When the fluidity and the hygroscopic solidificationpreventability of thus product were examined, the results were as shownin Table-l in the following. Example 3.

Through the same procedures as in Example 1, I00 parts by weight of ahollow-granular detergent having the following composition were coatedwith 2 parts by weight of calcium stearate having a mean particlediameter of less than 20p. by applying 1 part by weight of ethanol asthe binder. The result of examination of the properties of the productwas as shown in Table-l in the following.

Composition of the material hollow-granular detergent:

sodium olefin sulfonate having l3-l8 carbon atoms l! g sodiumtripoliphosphate 20 g sodium silicate g sodium sulfate 43 g fluorescentagent 0.4 g CMC 0.6 g water 9 g EXAMPLE 4.

sodium olefin sull'onate having l5-l8 carbon atoms l8 g sodiumtripoliphosphate g sodium silicate l0 g sodium sulfate 42 g fluorescentagent 0.4 g CMC 0.6 g water 9 g EXAMPLE 5.

Through the same procedures as in Example 1, l00 parts by weight of ahollow-granular detergent having the same composition as in Example 1were coated with 3 parts by weight of calcium stearate (consisting of 20wt.% of particles having a mean diameter of 50-30u and 80 wt.% ofparticles having a mean diameter of less than 30p.) by applying 1 partby weight of ethanol. The inside temperature of the rolling-drum on thisoccasion was 40C. The result of examination of the properties of theproduct was as shown in Table-l in the following.

EXAMPLE 6.

Through the same procedures as in Example 1, 100 parts by weight of ahollow-granular detergent having the same composition as in Example 1were coated with 1 part by weight of magnesium stearate having a meanparticle diameter of less than 10p instead of calcium stearate used inExample 1 and by applying 0.3 part by weight of ethylene glycol insteadof 0.5 part by weight of ethanol used in Example 1. The result ofexamination of the properties of the product was as shown in Table-l inthe following.

EXAMPLE 7.

Through the same procedures as in Example I, parts by weight of ahollow-granular detergent having the following composition were coatedwith 2 parts by weight of calcium stearate having a mean particlediameter of less than 10p by applying 0.5 part by weight of methanol asthe binder. The result of examination of the properties of the productwas as shown in Table-1 in the following.

Composition of the material hollow-granular detergent:

sodium linear alkylbenzene sulfonate 30 g sodium sulfate 65 g water 5 8EXAMPLE 8.

sodium linear alkylbenzene sulfonate 20 g sodium tripoliphosphate 22 gsodium silicate 10 g sodium sulfate 38 g fluorescent agent 0.4 g CMC 0.6g water 9 g EXAMPLE 9.

[n the same way as in Example 2 except for substituting magnesiumstearate for calcium stearate, a hollowgranular detergent product wasobtained. The result of examination of the properties of this productwas as shown in Table-l in the following.

EXAMPLE l0.

Through the same procedures as in Example l, 100 parts by weight of thesame material hollow-granular detergent as in Example 1 were coated with3 parts by weight of calcium stearate having a mean particle diameter ofless than 20p. by applying 0.2 part by weight of a perfume (namely,eugenol). The result of examination of the properties of the product wasas shown in Table-l in the following.

Table 1 Example No.

Rem arlrs:

Measurement of the fluidity was conducted by setting the temperature ofthe sample (product) at 35"C. "The hygroscopic solidificationpreventahility was evaluated through the procedure comprising leavingthe sample standing with atmosphere of 95% in RH and 30C in 24 hrs. thensifting this sample by the use ol'a 4-mcsh sieve. and

measuring the amount of sample left on the sieve in terms of wt.%.

'"The l'ragrancy was evaluated through the procedure comprising packingthe sample in a carbon case. leaving the thus packed sample standing ina room of normal temperature upon cutting open the prescribed outlet ofthe carton case. and counting the number of days required for half decayof the initial fragrancy after packing.

(The above procedures for measurement and evaluation will apply to thefollowing comparative examples too.)

Comparative Example 1.

The same material hollow-granular detergent as used in Example I wasleft standing for 24 hours without applying the treatment according tothe present invention, and was thereafter subjected to examination ofthe fluidity and hygroscopic solidification prevcntability thereof. Theresult was as shown in Table-2 in the following.

Comparative Example 2.

in the same .way as in Example 1 except for changing the amount ofcalcium stearate from 1 part by weight to 2 parts by weight and theparticle diameter thereof to be less than 1041 and substituting waterfor ethanol, coating of the material hollow-granular detergent wasefi'ected. The result of examination of the properties of the productwas as shown in Table-2 in the following.

Comparative Example 3.

[n the same way as in Example 1 except for substituting sodium sulfate(applied amount: 2 parts by weight; mean particle diameter: less than100p) for calcium stearate, coating of the material hollow-granulardetergent was effected. The result of examination of the properties ofthe product was as shown in Table-2 in the following.

Comparative Example 4.

In the same way as in Example 1 except for substituting sodium sulfate(applied amount: 2 parts by weight) for calcium stearate and 0.2 part byweight of geraniol for 0.5 part by weight of ethanol, coating of thematerial hollow-granular detergent was effected. The result ofexamination of the properties of the product was as shown in Table-2 inthe following.

Comparative Example 5.

0.2 part by weight of geraniol was added to 100 parts by weight of thesame material hollow-granular detergent as used in Example 1. The resultof examination of the properties of the product was as shown in Table-2in the following.

Table 2 Comparative Example No. l 2 3 4 5 fluidity (angle of repose) 4240 38 40' 42 hygroscopic solidification 25 27 30 20 25 preventabilityiragran 32 30 what is claimed is:

1. A process for improving the properties of granulated detergents,which comprises adding a lower alcohol or liquid perfume to an ordinaryhollow granular detergent produced by the spray drying method when thetemperature of the detergent is lower than the boiling point of thealcohol or perfume while making the detergent grains roll over, andsubsequently adding thereto a powder of a water insoluble metal soaphaving a mean particle diameter of less than when the surface of thegrains has been imparted with sufficicnt adhesive power by the additionof the alcohol or perfume.

2. A process according to claim 1, wherein said lower alcohol is atleast one member selected from the group consisting of monohydricalcohols having 1-4 carbon atoms and dihydric alcohols having 2-3 carbonatoms and the amount of said lower alcohol added is in the range of0.1-1 part by weight relative to 100 parts by weight of the detergent.

3. A process according to claim I, wherein said liquid perfume is amember selected from the group consisting of linalool, terpinneol,geraniol, eugenol, phenylethyl alcohol, benzyl alcohol and mixturesthereof and the amount of said liquid perfume added is in the range of0.05-1 part by weight relative to 100 parts by weight of the detergent.

4. A process according to claim 1, wherein said metallic soap isselected from the group consisting of calcium and magnesium salts ofsaturated fatty acids having at least 16 carbons and the amount of saidmetallic soap added is in the range of 0.3-1 5 parts by weight relativeto 100 parts by weight of the detergent.

1. A PROCESS FOR IMPROVING THE PROPERTIES OF GRANULATED DETERGENTS, WHICH COMPRISES ADDING A LOWER ALCOHOL OR LIQUID PERFUME TO AN ORDINARY HOLLOW GRANULAR DETERGENT PRODUCED BY THE SPRAY DRYING METHOD WHEN THE TEMPERATURE OF THE DETERGENT IS LOWER THAN THE BOILING POINT OF THE ALCOHOL OR PERFUME WHILE MAKING THE DETERGENT GRAINS ROLL OVER, AND SUBSEQUENTLY ADDING THERETO A POWDER OF A WATER INSOLUBLE METAL SOAP HAVING A MEAN PARTICLE DIAMETER OF LESS THAN 100U WHEN THE SURFACE OF THE GRAINS HAS BEEN IMPARTED WITH SUFFICIENT ADHESIVE POWER BY THE ADDITION OF THE ALCOHOL OR PERFUME.
 2. A process according to claim 1, wherein said lower alcohol is at least one member selected from the group consisting of monohydric alcohols having 1-4 carbon atoms and dihydric alcohols having 2-3 carbon atoms and the amount of said lower alcohol added is in the range of 0.1-1 part by weight relative to 100 parts by weight of the detergent.
 3. A process according to claim 1, wherein said liquid perfume is a member selected from the group consisting of linalool, terpinneol, geraniol, eugenol, phenylethyl alcohol, benzyl alcohol and mixtures thereof and the amount of said liquid perfume added is in the range of 0.05-1 part by weight relative to 100 parts by weight of the detergent.
 4. A process according to claim 1, wherein said metallic soap is selected from the group consisting of calcium and magnesium salts of saturated fatty acids having at least 16 carbons and the amount of said metallic soap added is in the range of 0.3-15 parts by weight relative to 100 parts by weight of the detergent. 